HDO and D2O long path spectroscopy: Ongoing work of the ... · HDO+D 2O H 2O D 2O H 2O+HDO Path:...
Transcript of HDO and D2O long path spectroscopy: Ongoing work of the ... · HDO+D 2O H 2O D 2O H 2O+HDO Path:...
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Ludovic DaumontLudovic Daumont
Groupe Groupe de de Spectroscopie Moléculaire Spectroscopie Moléculaire et et AtmosphériqueAtmosphérique
UMR CNRS 6089 UMR CNRS 6089
UniversitéUniversité de de Reims Reims Champagne Champagne ArdenneArdenne
ReimsReims, France, France
HDO and D2O long path spectroscopy: Ongoing work of the Brussels-Reims
Team.
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Workgroup involved in water vaporWorkgroup involved in water vaporabsorption measurementsabsorption measurements
•• L.L. DaumontDaumont, (M, (M--F. F. MérienneMérienne), L.Regalia), L.Regalia--JarlotJarlot,, VlVl.. TyuterevTyuterev, A. , A. JenouvrierJenouvrierGroupeGroupe dede Spectrométrie MoléculaireSpectrométrie Moléculaire etet AtmosphériqueAtmosphériqueUniversitéUniversité dede ReimsReims ChampagneChampagne--ArdenneArdenne.. ReimsReims, France, France
•• S. S. FallyFally, P, P--F. F. CoheurCoheur, C. , C. ClerbauxClerbaux, M. Bach, M. , M. Bach, M. CarleerCarleerUnitéUnité de de SpectroscopieSpectroscopie AtmosphériqueAtmosphériqueService de Service de ChimieChimie QuantiqueQuantique et et PhotophysiquePhotophysiqueUniversité LibreUniversité Libre de de BruxellesBruxelles. Brussels, Belgium. Brussels, Belgium
•• AA--C. C. VandaeleVandaele, C. , C. HermansHermansInstitutInstitut d’Aéronomied’Aéronomie SpatialeSpatiale de de BelgiqueBelgique. . BruxellesBruxelles, , BelgiqueBelgique
•• A. A. CampargueCampargueLaboratoireLaboratoire de de Spectrométrie Spectrométrie PhysiquePhysiqueUniversitéUniversité de de GrenobleGrenoble, Saint, Saint--MartinMartin--d’Hèresd’Hères, France, France
•• S. S. MikhailenkoMikhailenko, O., O. NaumenkoNaumenko, S. , S. TachkunTachkunInstitut Institut of Atmospheric Optics, of Atmospheric Optics, TomskTomsk, Russia, Russia
•• J.TennysonJ.TennysonDepartment of Physics and Astronomy, University College, EngDepartment of Physics and Astronomy, University College, Englandland
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1E-22
1E-17
0 5000 10000 15000 20000 250001E-27
1E-22
1E-17
1E-22
1E-17
1E-22
1E-17
Band Centers cm-1
Inte
grat
edab
sorp
tion
cros
s se
ctio
ns
ΣS(2
96K
) cm
/mol
ec
HOD
H217O
H218O
H216O
HITRAN 2004HITRAN 2004
7250 cm-1
10012 cm-1
13780 cm-1
25120 cm-1
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Experimental setupExperimental setup
Sources Xe, W, Globar
Cell (50 m base long )
Cooling or heating system
Temperature controlled Cell(5 m base long )
Laboratory made Spectrometer
Bruker FTSIFS 120M
(ULB or IASB)
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Experimental setupExperimental setup
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•• Absorption path: 600 m Absorption path: 600 m
•• Resolution: down to 0.03 cmResolution: down to 0.03 cm--11 (30 cm MOPD)(30 cm MOPD)
•• Spectral range: 8800 Spectral range: 8800 -- 10200 cm10200 cm--11
•• HH22O + DO + D22OO mixturesmixtures (( PPtot tot ∼∼ 1010 hPahPa ))
••Room temperature: TRoom temperature: T∼∼ 293 K293 K
••WavenumberWavenumber calibration:calibration: II22 ( table of( table of GesternkornGesternkorn ))
experimental conditionsexperimental conditionsfor HDO for HDO –– DD22O spectraO spectra
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diode GaPXe Source
diode SiW Source
7ν+δ
8ν
7ν
6ν+δ 5ν+δ
6ν
5ν
4ν
4ν+δ 3ν
3ν+δ
2ν+δ
diode SiXe Source
VisVis--NIR water absorption spectraNIR water absorption spectra
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IR Absorption spectraIR Absorption spectra
diode SiW Source
InSbW Source
InSbW Source
2ν+δ 2ν ν+δν
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Observed (H2O & HOD)
Inte
nsity
(a. u
.)
Simulated (H2O)
15260 15258 15256 15254 15252 15250 15248 15246 15244 15242 15240
Subtracted (only HOD lines left)
Wavenumber (cm-1)
VisVis--NIR spectral range: NIR spectral range: Subtraction of the HSubtraction of the H22O linesO lines
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85009000950010000105001100011500
0.5
1
1.5
2
910091059110911591209125
0.4
0.9
1.4
1.9
2.4
H2O pure
H2O:3.1%HDO:22.7%D2O:74.2 %
H2O:16.5 %HDO:49.8 %D2O:33.7 %
A
B
C
A / C
C / B
NIR spectral range:NIR spectral range:HH22O, HDO O, HDO andand DD22OO
HDO+D2O
H2O
D2O
H2O+HDO
PathPath: 600 m, P: 13 : 600 m, P: 13 hPahPa, , ResolResol.: 0.03 cm.: 0.03 cm--11
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Partial pressures: IR Partial pressures: IR regionregion•Total Pressures: Baratron Ptot1=P1161+P1261+P2261 Ptot2=P1162+P1262+P2262
•Use of BR list for H216O partial pressures (from natural H2O spectra)
Ptot1=P1161+P1261+P2261 Ptot2=P1162+P1262+P2262
•Isotopologue assignement => Spectra Ratios
•Line surface measurements => with the good molar mass
•Determination of the mean Surface ratios for HDO and D2O
r1=P1261/P1262 r2=P2261/P2262
• Calculation of partial pressures and line intensities
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0
2E-24
4E-24
6E-24
8E-24
1E-23
1.2E-23
8800 8900 9000 9100 9200 9300 9400 9500 9600
*
*
*
*
**
*
0
2E-24
4E-24
6E-24
8E-24
1E-23
1.2E-230
2E-24
4E-24
6E-24
8E-24
1E-23
1.2E-23
H20
D2O
HDO
IR IR regionregion: :
HH220, D0, D220 0 andand HDO line HDO line intensitiesintensities
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IR IR regionregion: HDO line assignement: HDO line assignementBased on the new calculation of Partridge and Schwenke for both positions and intensities
Still under progress in this region (8800-10200 cm-1)
In the present work
HDO 8800-10200 cm-1 region:
4380 observed lines mainly from 2ν+δ, 3ν and 3ν+δ polyads
5200 assignments
An integrated intensity of 2 10-21 cm molec-1 for this region
D2O: 8800- 13200 cm-1 region:
2160 observed lines mainly from 3ν+δ, 4ν, 4ν+δ and 5ν polyads
2596 assignements
An integrated intensity of 8 10-22 cm molec-1 for this region
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Example of aExample of a subbandsubband::νν11+2 +2 νν3 3
∆∆KKaa=0 K=0 K””aa=0=0
9700 9800 9900 10000 101000
4
8
Wavenumber cm-1
-0.10
-0.05
0.00
0
1
2
S(obs)S(PS)
νν obsob
s-- νν c
alc
calc
(cm
(cm
-- 11))
S (1
0-24
cm m
olec
-1)
∆∆KKcc==--11 ∆∆KKcc=1=1Average: 0.95
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9800 9900 10000 101000
1
2
-0.2
-0.1
0.0
1
2
Example II of aExample II of a subbandsubband::νν11+2 +2 νν3 3
∆∆KKaa=1 K=1 K””aa=0, =0, ∆∆KKcc=1 =1
S(obs)S(PS)
νν obsob
s-- νν c
alc
calc
(cm
(cm
-- 11))
S (1
0-24
cm m
olec
-1)
Average: 0.97
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•• Entire spectral range Entire spectral range →→ Better agreement between different spectral Better agreement between different spectral ranges.ranges.
•• A lot of weak lines A lot of weak lines →→ Better atmospheric spectra simulation.Better atmospheric spectra simulation.
•• Convergence of the theory towards the experimental needs.Convergence of the theory towards the experimental needs.
•• The discrete bands can now be taken off to study the underlyingThe discrete bands can now be taken off to study the underlyingcontinuum.continuum.
•• A lot of unresolved blended lines A lot of unresolved blended lines
••Water vapor pressure measurement still difficult.Water vapor pressure measurement still difficult.
•• Longer absorption paths needed to compare to atmospheric horizoLonger absorption paths needed to compare to atmospheric horizontal ntal (10 (10 -- 20 km) measurement at sea level !20 km) measurement at sea level !
Global commentsGlobal comments
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Available Available linelistslinelists and intensitiesand intensities
Continuing workContinuing work
•• IUPACIUPAC-- Water vapor database constitution for all the Water vapor database constitution for all the isotopologues isotopologues
(experience and theory)(experience and theory)•• HODHOD-- DD22OO
-- Measures down to 4200 cmMeasures down to 4200 cm--1 1 (spectra being processed)(spectra being processed)•• HH22OO
-- Analysis of the IR spectra (6600 Analysis of the IR spectra (6600 –– 8800 cm8800 cm--11))•• HH221818OO
-- …..…..
•• web site fromweb site from ULBULB-- http://www.http://www.ulbulb.ac.be/.ac.be/cpmcpm//datafilesdatafiles.html.html
•• HITRAN 2004HITRAN 2004-- http://http://cfacfa--www.www.harvardharvard..eduedu/HITRAN/HITRAN
•• GEISA 2003GEISA 2003-- http://http://araara..lmdlmd..polytechniquepolytechnique..frfr
http://ara.lmd.polytechnique.fr/
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IR Absorption spectraIR Absorption spectra
diode SiW Source
InSbW Source
InSbW Source
2ν+δ 2ν ν+δν
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The EndThe End
HDO and D2O long path spectroscopy: On going work of the Brussels-Reims
Team.
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